WO2016104173A1 - Dispositif à semi-conducteurs, dispositif d'imagerie à semi-conducteurs, et dispositif électronique - Google Patents

Dispositif à semi-conducteurs, dispositif d'imagerie à semi-conducteurs, et dispositif électronique Download PDF

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WO2016104173A1
WO2016104173A1 PCT/JP2015/084739 JP2015084739W WO2016104173A1 WO 2016104173 A1 WO2016104173 A1 WO 2016104173A1 JP 2015084739 W JP2015084739 W JP 2015084739W WO 2016104173 A1 WO2016104173 A1 WO 2016104173A1
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film
organic
layer
photoelectric conversion
state imaging
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Japanese (ja)
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利彦 林
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ソニー株式会社
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    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
    • H04N25/00—Circuitry of solid-state image sensors [SSIS]; Control thereof
    • H04N25/70—SSIS architectures; Circuits associated therewith
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/30—Devices controlled by radiation
    • H10K39/32—Organic image sensors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present disclosure relates to a semiconductor device, a solid-state imaging device, and an electronic device, and more particularly, to a semiconductor device, a solid-state imaging device, and an electronic device that can improve the reliability of an organic photoelectric conversion layer.
  • the organic material layer has been attracting attention in recent years for its application to various electronic devices because it is easy to adjust the composition and properties, and can be formed by a coating method or an inkjet method.
  • a photoelectric conversion region for photoelectrically converting light of each wavelength of green, blue, and red is stacked in the vertical direction of the same pixel, and the green photoelectric conversion region is configured by an organic photoelectric conversion film.
  • a solid-state imaging device has been proposed. If such a structure is used, there is an advantage that light loss does not occur in the color filter, and an effect that no false color is generated because interpolation processing is not performed can be expected.
  • the signal readout circuit on the semiconductor substrate side is manufactured in the same manner as a conventional CCD-type or CMOS-type image sensor. Yes, the manufacturing technology of the semiconductor device can be used as it is.
  • the photoelectric conversion film which is an organic material layer laminated on the semiconductor substrate, and the electrode film and the insulating film sandwiching the photoelectric conversion film can also be obtained by using a vacuum deposition method, a sputtering method, a CVD (Chemical Vapor Deposition) method, etc. It can be manufactured easily.
  • Patent Document 1 proposes a film configuration between an organic photoelectric conversion layer and an electrode positioned on the organic photoelectric conversion layer.
  • the reliability of organic semiconductor films deteriorates even if a small amount of moisture is taken in, it is necessary to form an electrode film under a high vacuum, and a formation method other than sputtering under vacuum In the case of removing the film, the organic material is limited to an organic material having high durability against the air atmosphere.
  • the present disclosure has been made in view of such a situation, and can improve the reliability of the organic photoelectric conversion layer.
  • a semiconductor device includes an oxygen blocking layer that suppresses oxygen from entering the organic film between the organic film and the organic film and a metal oxide formed above the organic film.
  • the oxygen blocking layer is an inorganic fluoride that has low reactivity with oxygen.
  • the oxygen blocking layer is transparent in the visible light range.
  • the oxygen blocking layer is made of MgF2, CaF2, BaF2, LiF or a three-dimensional compound containing any of the MgF2, CaF2, BaF2, and LiF.
  • a stabilization layer which is an inorganic film having a higher standard generation energy than the oxygen blocking layer, may be further provided between the organic film and the oxygen blocking layer.
  • the stabilization layer is made of Li, Co, or Ni.
  • the thickness of the oxygen blocking layer is thicker than that of the stabilization layer.
  • the metal oxide is formed by a sputtering method.
  • the organic film is used as an organic photoelectric conversion film.
  • the organic film is used as an organic EL film.
  • the solid-state imaging device is an oxygen blocking device that suppresses oxygen from entering the organic film between the organic film and the organic film and a metal oxide formed above the organic film. A layer.
  • the oxygen blocking layer is an inorganic fluoride that has low reactivity with oxygen.
  • the oxygen blocking layer is transparent in the visible light range.
  • the oxygen blocking layer is made of MgF2, CaF2, BaF2, LiF or a three-dimensional compound containing any of the MgF2, CaF2, BaF2, and LiF.
  • a stabilization layer which is an inorganic film having a higher standard generation energy than the oxygen blocking layer, may be further provided between the organic film and the oxygen blocking layer.
  • the stabilization layer is made of Li, Co, or Ni.
  • the thickness of the oxygen blocking layer is thicker than that of the stabilization layer.
  • the metal oxide is formed by a sputtering method.
  • the electronic device is an oxygen blocking layer that suppresses oxygen from entering the organic film between the organic film and the organic film and a metal oxide formed above the organic film.
  • a solid-state imaging device a signal processing circuit that processes an output signal output from the solid-state imaging device, and an optical system that makes incident light incident on the solid-state imaging device.
  • an oxygen blocking layer that suppresses oxygen from entering the organic film is provided between the organic film and the metal oxide formed above the organic film.
  • the reliability of the organic photoelectric conversion layer can be improved.
  • First embodiment (example of solid-state imaging device) 2.
  • Second embodiment (example of EL device) 3.
  • Third embodiment (use example of image sensor) 4).
  • Fourth embodiment (an example of an electronic device)
  • FIG. 1 illustrates a schematic configuration example of an example of a complementary metal oxide semiconductor (CMOS) solid-state imaging device applied to each embodiment of the present technology.
  • CMOS complementary metal oxide semiconductor
  • a solid-state imaging device (element chip) 1 includes a pixel region (a pixel region in which pixels 2 including a plurality of photoelectric conversion elements are regularly arranged two-dimensionally on a semiconductor substrate 11 (for example, a silicon substrate). A so-called imaging region) 3 and a peripheral circuit section.
  • the pixel 2 includes a photoelectric conversion element (for example, a photodiode) and a plurality of pixel transistors (so-called MOS transistors).
  • the plurality of pixel transistors can be constituted by three transistors, for example, a transfer transistor, a reset transistor, and an amplifying transistor, and can further be constituted by four transistors by adding a selection transistor. Since the equivalent circuit of each pixel 2 (unit pixel) is the same as a general one, detailed description thereof is omitted here.
  • the pixel 2 can have a shared pixel structure.
  • the pixel sharing structure includes a plurality of photodiodes, a plurality of transfer transistors, one shared floating diffusion, and one other pixel transistor that is shared.
  • the peripheral circuit section includes a vertical drive circuit 4, a column signal processing circuit 5, a horizontal drive circuit 6, an output circuit 7, and a control circuit 8.
  • the control circuit 8 receives data for instructing an input clock, an operation mode, and the like, and outputs data such as internal information of the solid-state imaging device 1. Specifically, the control circuit 8 is based on the vertical synchronization signal, the horizontal synchronization signal, and the master clock, and the clock signal or the reference signal for the operations of the vertical drive circuit 4, the column signal processing circuit 5, and the horizontal drive circuit 6 Generate a control signal. The control circuit 8 inputs these signals to the vertical drive circuit 4, the column signal processing circuit 5, and the horizontal drive circuit 6.
  • the vertical drive circuit 4 is composed of, for example, a shift register, selects a pixel drive wiring, supplies a pulse for driving the pixel 2 to the selected pixel drive wiring, and drives the pixels 2 in units of rows. Specifically, the vertical drive circuit 4 selectively scans each pixel 2 in the pixel region 3 sequentially in the vertical direction in units of rows, and generates the signal according to the amount of light received by the photoelectric conversion element of each pixel 2 through the vertical signal line 9. A pixel signal based on the signal charge is supplied to the column signal processing circuit 5.
  • the column signal processing circuit 5 is disposed, for example, for each column of the pixels 2 and performs signal processing such as noise removal on the signal output from the pixels 2 for one row for each pixel column. Specifically, the column signal processing circuit 5 performs signal processing such as CDS (Correlated Double Sampling) for removing fixed pattern noise specific to the pixel 2, signal amplification, A / D (Analog / Digital) conversion, and the like. .
  • a horizontal selection switch (not shown) is provided connected to the horizontal signal line 10.
  • the horizontal drive circuit 6 is constituted by, for example, a shift register, and sequentially outputs horizontal scanning pulses to select each of the column signal processing circuits 5 in order, and the pixel signal is output from each of the column signal processing circuits 5 to the horizontal signal line. 10 to output.
  • the output circuit 7 performs signal processing on the signals sequentially supplied from each of the column signal processing circuits 5 through the horizontal signal line 10 and outputs the signals.
  • the output circuit 7 may perform only buffering, or may perform black level adjustment, column variation correction, various digital signal processing, and the like.
  • the input / output terminal 12 is provided for exchanging signals with the outside.
  • FIG. 2 is a cross-sectional view illustrating an example of an organic photoelectric conversion unit as a semiconductor device to which the present technology is applied.
  • the organic photoelectric conversion unit 21 is configured to include an upper electrode film 31, an organic photoelectric conversion layer 32, and a lower electrode film 33.
  • the upper electrode film 31 and the lower electrode film 33 are transparent metal oxide films, and are made of, for example, sputtered films containing oxygen.
  • the upper electrode film 31 and the lower electrode film 33 are made of a conductive film having transparency, and are made of a metal oxide such as ITO (indium tin oxide), for example.
  • a metal oxide such as ITO (indium tin oxide), for example.
  • ITO indium tin oxide
  • a tin oxide (SnO2) -based material added with a dopant, or a zinc oxide-based material obtained by adding a dopant to aluminum zinc oxide (ZnO) may be used.
  • zinc oxide-based materials include aluminum zinc oxide (AZO) added with aluminum (Al) as a dopant, gallium zinc oxide (GZO) added with gallium (Ga), and indium zinc oxide added with indium (In). (IZO).
  • CuI, InSbO4, ZnMgO, CuInO2, MgIn2O4, CdO, ZnSnO3, etc. may be used.
  • the organic photoelectric conversion layer 32 includes an oxygen blocking layer 41, a stabilization layer 42, an organic photoelectric conversion film 43, and a hole readout layer 44 in order from the top.
  • oxygen to the organic photoelectric conversion unit 21 is interposed between the organic photoelectric conversion film 43 and the upper electrode film 31 that is a layer on which the metal oxide on the organic photoelectric conversion film 43 is installed.
  • An oxygen blocking layer 41 that blocks (suppresses) entry and a stabilization layer 42 are provided in order from the top.
  • the oxygen blocking layer 41 is made of, for example, a transparent inorganic fluoride that has low reactivity with oxygen.
  • the oxygen blocking layer 41 is transparent in the visible light region and is thicker than the stabilization layer 42.
  • the stabilization layer 42 is composed of an inorganic film having a standard generation energy larger than that of the oxygen blocking layer 41.
  • the organic photoelectric conversion film 43 is an organic film that converts light into an electric signal, and is made of a p-type photoelectric conversion material.
  • the hole readout layer 44 reads out holes (holes) of the electric signal converted by the organic photoelectric conversion film 43.
  • the p-type photoelectric conversion material contained in the organic photoelectric conversion film 43 preferably has at least one of a hole transport property and an electron transport property regardless of the wavelength to be absorbed.
  • p-type photoelectric conversion materials are quinacridone derivatives, phthalocyanine derivatives, porphyrin derivatives, squarylium derivatives, naphthalene or perylene derivatives, cyanine derivatives, merocyanine derivatives, rhodamine derivatives, diphenylmethane or triphenylmethane derivatives, xanthene derivatives, acridine derivatives, phenoxazines.
  • quinoline derivatives oxazole derivatives, thiazole derivatives, oxazine derivatives, thiazine derivatives, benzoquinone derivatives, naphthoquinone derivatives, anthraquinone derivatives, indigo or thioindigo derivatives, pyrrole derivatives, pyridine derivatives, dipyrine derivatives, indole derivatives, diketopyrrolopyrrole derivatives, coumarins
  • fluorene derivatives fluoranthene derivatives, anthracene derivatives, pyrene derivatives
  • Triarylamine derivatives such as triphenylamine, naphthylamine and styrylamine, carbazole derivatives, phenylenediamine derivatives or benzidine derivatives, phenanthroline derivatives, imidazole derivatives, oxazoline derivatives, thiazoline derivatives, triazole derivatives, thiadiazole derivatives,
  • the p-type photoelectric conversion material may be a linked body, a multimer, a polymer, a copolymer, a block copolymer, or the like having the above-described substituent as a unit structure.
  • a quinacridone derivative is preferable as the p-type photoelectric conversion material included in the photoelectric conversion film according to the embodiment of the present disclosure.
  • the thickness of such an organic photoelectric conversion film 43 is, for example, 50 nm to 250 nm.
  • a method for forming a thin film there are a spin coating method and a coating method by an ink jet method, but a vacuum vapor deposition method is most suitable because material characteristics are easily obtained.
  • an oxide target for example, When an ITO film is formed using In 2 O 3 / SnO 2
  • oxygen ions (O ⁇ ) and recoil Ar particles fly on the organic photoelectric conversion film 43.
  • Oxygen ions (O ⁇ ) cause an impurity level in the organic photoelectric conversion film 43 due to the reaction with the organic photoelectric conversion film 43, resulting in characteristic deterioration.
  • an oxygen blocking layer 41 that is a transparent fluoride layer having low reactivity with oxygen is inserted between the organic photoelectric conversion film 43 and the upper electrode film 31.
  • Fluoride materials that do not easily cause bond dissociation due to incident particle energy are desirable, and candidates include the following materials having a lattice energy of 10 eV or more.
  • the candidate material is not limited below, and may be a ternary compound including the following materials.
  • Fluoride has a concern that fluorine may be detached and diffused into the organic photoelectric conversion film 43 under the influence of the manufacturing process or under a long-term use environment.
  • an element having a larger standard generation energy than the constituent elements of the fluoride described above is installed as the stabilization layer 42 between the organic photoelectric conversion film 43 and the fluoride. Thereby, the entry of fluorine from the fluoride is suppressed.
  • FIG. 4 shows element candidates with high standard generation energy when the fluoride is MgF2.
  • Candidates for the stabilizing layer 42 include Be, Pb, Sb, Cr, Zn, Fe, Co, Ni, Li, Ir, Na, K, Rb, Cs, Cu, Tl, and Xe.
  • the oxygen blocking layer 41 (fluoride layer) has a minimum of 10 nm or more because sputtered particle ions enter. It is desirable to be.
  • the stabilization layer is preferably thin from the viewpoint of deterioration of transmittance since a single element is inserted, and from the viewpoint of preventing diffusion of fluorine, a certain film thickness is required and is preferably 3 nm or less.
  • a resistance heating vapor deposition method and an electron ion beam method can be cited because they can be formed continuously with an organic semiconductor film under vacuum and can be formed with low energy.
  • the oxygen blocking layer 41 that is a layer using a fluoride material that suppresses the oxidation reaction to the organic photoelectric conversion film 43 is provided.
  • the metal oxide film (upper electrode film 31) using the sputtering method, reaction between oxygen and the organic film is prevented, and decomposition of the organic photoelectric conversion film 43 and dissociation of bonds are suppressed.
  • an inorganic film (stabilization layer 42) having a large standard generation energy is provided under the layer using the fluoride material (oxygen blocking layer 41), diffusion of fluorine from the fluoride is prevented, and organic Fluorine can be prevented from entering the photoelectric conversion film 43.
  • FIG. 5 is a cross-sectional view illustrating an example of the overall configuration of a solid-state imaging device having the photoelectric conversion unit of FIG.
  • a plurality of pixels 2 made of, for example, organic photoelectric conversion elements are formed in the pixel region 3, and a peripheral circuit for driving each pixel 2 is formed in the peripheral circuit unit SC.
  • the solid-state imaging device 1 includes pixel transistors (including transfer transistors Tr1 to Tr3) on the surface (surface S2 opposite to the light receiving surface S1) of the semiconductor substrate 11, and a multilayer wiring layer (multilayer wiring layer 61). ) Having a so-called back-illuminated structure.
  • the organic photoelectric conversion unit 21 of FIG. 2 has a lower electrode film 33 on the semiconductor substrate 11 via interlayer insulating films 52A and 52B.
  • the lower electrode film 33 is disposed in a selective region on the semiconductor substrate 11, and the interlayer insulating films 52A and 52B are electrically connected to the lower electrode film 33 and a wiring layer (not shown).
  • the conductive plugs 52a2, 52a3, 52b2, and 52b3 are embedded.
  • An insulating film 53 having an opening is provided on the semiconductor substrate 11 so as to face the lower electrode film 33, and the organic photoelectric conversion layer 32 is formed in the opening of the insulating film 53.
  • the insulating film 53 has a groove 56 in a region different from such an opening (a region not facing the lower electrode film 33), and the organic photoelectric conversion layer 32 is insulated from the inside of the opening of the insulating film 53.
  • the film 53 extends to the groove 56 and is divided at the groove 56.
  • the upper electrode film 31 and the sealing film 54 are laminated on the organic photoelectric conversion layer 32 in this order.
  • a contact metal layer 55 is formed so as to cover the end portions of the upper electrode film 31 and the sealing film 54.
  • the contact metal layer 55 is connected to a wiring layer (not shown) via, for example, a wiring layer 51 disposed in the same layer as the lower electrode film 33 and conductive plugs 52b2 and 52b3 embedded in the interlayer insulating film 52B.
  • a wiring layer 51 disposed in the same layer as the lower electrode film 33 and conductive plugs 52b2 and 52b3 embedded in the interlayer insulating film 52B.
  • the semiconductor substrate 11 is made of, for example, silicon (Si). However, depending on the use of the organic photoelectric conversion part 21, it may be comprised with glass, plastic, or the metal plate by which the surface was insulated.
  • the conductive plugs 52 a 2, 52 a 3, 52 b 2, and 52 b 3 function as connectors to the semiconductor substrate 11.
  • These conductive plugs 52a2, 52a3, 52b2, and 52b3 are preferably formed of a laminated film of materials such as titanium (Ti), titanium nitride (TiN), and tungsten (W).
  • the interlayer insulating films 52A and 52B reduce the interface state with the semiconductor substrate 11 (Si) and reduce the generation of dark current from the interface with the silicon layer 11S. It is desirable to be configured to include.
  • a stacked film in which a hafnium oxide (Hfo2) film and a silicon compound film are formed in this order from the semiconductor substrate 11 side can be used.
  • the silicon compound film for example, a single layer film made of any one of a silicon oxide (Sio2) film, a silicon nitride (SiN) film, and a silicon oxynitride film (SiON), or a laminated film made of two or more of them.
  • a membrane can be used.
  • the insulating film 53 is composed of, for example, a single layer film made of one of silicon oxide, silicon nitride, silicon oxynitride, and aluminum oxide (AlOx), or a laminated film made of two or more of these. Yes.
  • the insulating film 53 has a function of electrically separating the lower electrode films 33 of the respective pixels when the organic photoelectric conversion unit 21 is used in the solid-state imaging device 1.
  • a film having low water permeability and moisture absorption is desirable. Examples of such a material include silicon nitride and aluminum oxide.
  • the material is preferably a material that takes into account a reflection component due to optical interference with the upper electrode film 31 (transparent conductive film).
  • the upper electrode film 31 transparent conductive film
  • silicon nitride may be used. This is because ITO and silicon nitride are close in refractive index, so that the interference effect can be easily reduced.
  • the groove 56 forms a step on the surface of the insulating film 53 and divides the organic photoelectric conversion layer 32 by this step.
  • the groove 56 penetrates to the upper surface of the stopper 51c formed in the same layer as the lower electrode film 33 in the boundary region between the pixel region 3 of the insulating film 53 and the peripheral circuit portion SC. Is provided.
  • the stopper 51c controls the depth of the groove 56, and is made of the same material as the lower electrode film 33, for example.
  • the stopper 51c can be formed at the same time when the lower electrode film 33 is formed in a pattern.
  • the organic photoelectric conversion layer 32 includes an oxygen blocking layer 41, a stabilization layer 42, an organic photoelectric conversion film 43, and a hole readout layer 44 in order from the top.
  • the upper electrode film 31 is formed so as to be connected in a region facing the groove 56.
  • the thickness of the upper electrode film 31 is, for example, 50 nm to 150 nm.
  • the sealing film 54 is formed on the upper electrode film 31 and is, for example, a single layer film made of one of silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide, or the like, or these It is the laminated film which consists of 2 or more types.
  • the sealing film 54 is formed so as to be connected to a region facing the groove 56 so as to cover the upper surface of the upper electrode film 31.
  • the end portion of the sealing film 54 region corresponding to the peripheral circuit portion SC
  • the thickness of the sealing film 54 is, for example, 100 nm to 1 ⁇ m.
  • the contact metal layer 55 is made of, for example, any one of titanium, tungsten, titanium nitride, aluminum and the like, or a laminated film made of two or more of them.
  • the pixel 2 in the pixel region 3 has a structure in which an organic photoelectric conversion unit that selectively detects light in different wavelength ranges and performs photoelectric conversion and an inorganic photoelectric conversion unit are stacked in the vertical direction. .
  • the pixel 2 has a stacked structure of one organic photoelectric conversion unit 21 and two inorganic photoelectric conversion units 11B and 11R, whereby red (R), green (G), and blue (B ) For each color signal.
  • the organic photoelectric conversion unit 21 is formed on the back surface (surface S ⁇ b> 1) of the semiconductor substrate 11, and the inorganic photoelectric conversion units 11 ⁇ / b> B and 11 ⁇ / b> R are embedded in the semiconductor substrate 11.
  • the configuration of each unit will be described.
  • the semiconductor substrate 11 is formed by embedding inorganic photoelectric conversion portions 11B and 11R and a green power storage layer 11G in a predetermined region of an n-type silicon (Si) layer 11S, for example.
  • conductive plugs 52 a 1 and 52 b 1 serving as transmission paths for charges (electrons or holes) from the organic photoelectric conversion unit 21 are embedded.
  • the back surface (surface S1) of the semiconductor substrate 11 can be said to be a light receiving surface.
  • a plurality of pixel transistors (including transfer transistors Tr1 to Tr3) corresponding to the organic photoelectric conversion unit 21 and the inorganic photoelectric conversion units 11B and 11R are formed on the surface (surface S2) side of the semiconductor substrate 11.
  • a plurality of pixel transistors (including transfer transistors Tr1 to Tr3) corresponding to the organic photoelectric conversion unit 21 and the inorganic photoelectric conversion units 11B and 11R are formed.
  • a peripheral circuit composed of a logic circuit or the like is formed.
  • Examples of the pixel transistor include a transfer transistor, a reset transistor, an amplification transistor, and a selection transistor.
  • Each of these pixel transistors is formed of a MOS transistor, for example, and is formed in the p-type semiconductor well region on the surface S2.
  • a circuit including such a pixel transistor is formed for each of the red, green, and blue photoelectric conversion units.
  • Each circuit may have a three-transistor configuration including a total of three transistors, such as a transfer transistor, a reset transistor, and an amplifying transistor, among these pixel transistors, or four transistors including a selection transistor. It may be a configuration.
  • the transfer transistors Tr1 to Tr3 are shown and described.
  • pixel transistors other than the transfer transistor can be shared between photoelectric conversion units or between pixels. Further, a so-called pixel sharing structure that shares a floating diffusion can also be applied.
  • the transfer transistors Tr1 to Tr3 include a gate electrode (three gate electrodes TG) and three floating diffusions (FD). Among these, the three gate electrodes TG are provided in the wiring layer 51, and the three FDs are formed in the semiconductor substrate 11.
  • the transfer transistor Tr1 transfers the signal charge corresponding to green (hole in the present embodiment) generated in the organic photoelectric conversion unit 21 and accumulated in the green power storage layer 11G to a vertical signal line Lsig described later. It is.
  • the transfer transistor Tr2 transfers the signal charge (here, hole) corresponding to blue generated and accumulated in the inorganic photoelectric conversion unit 11B to the vertical signal line Lsig.
  • the transfer transistor Tr3 transfers signal charges (holes in the present embodiment) corresponding to red color generated and accumulated in the inorganic photoelectric conversion unit 11R to the vertical signal line Lsig.
  • the inorganic photoelectric conversion units 11B and 11R are photodiodes having pn junctions (Photo-Diodes), and are formed in the order of the inorganic photoelectric conversion units 11B and 11R from the surface S1 side on the optical path in the semiconductor substrate 11.
  • the inorganic photoelectric conversion unit 11B selectively detects blue light and accumulates signal charges corresponding to blue. For example, from the selective region along the surface S1 of the semiconductor substrate 11, multiple layers are formed. It is formed to extend over a region near the interface with the wiring layer 61.
  • the inorganic photoelectric conversion unit 11R selectively detects red light and accumulates signal charges corresponding to red, and is formed, for example, over a region below the inorganic photoelectric conversion unit 11B (surface S2 side).
  • blue (B) is a color corresponding to a wavelength range of 450 m to 495 nm
  • red (R) is a color corresponding to a wavelength range of 620 nm to 750 nm, for example
  • the inorganic photoelectric conversion units 11B and 11R are It is only necessary that light in a part or all of the wavelength region can be detected.
  • the green electricity storage layer 11G is configured to include a p-type region serving as a hole accumulation layer, for example. A part of the p-type region is connected to the conductive plug 52a1, and accumulates holes transmitted from the lower electrode film 33 side through the conductive plug 52a1.
  • the conductive plug 52a1 is electrically connected to the lower electrode film 33 of the organic photoelectric conversion unit 21, and is connected to the green power storage layer 11G.
  • the conductive plug 52b1 is electrically connected to the upper electrode film 31 of the organic photoelectric conversion unit 21, and serves as a wiring for discharging electrons.
  • Each of these conductive plugs 52a1 and 52b1 is formed, for example, by burying a conductive film material such as tungsten in a through via.
  • a conductive film material such as tungsten
  • the via side surface be covered with an insulating film such as silicon oxide (SiO 2) or silicon nitride (SiN).
  • the conductive plugs 52a1 and 52b1 may be embedded with a conductive semiconductor layer.
  • the conductive plug 52a1 is preferably p-type (because it becomes a hole transmission path), and the conductive plug 52b1 is preferably n-type (because it becomes an electron transmission path).
  • a multilayer wiring layer 61 is formed on the surface S2 of the semiconductor substrate 11 as described above.
  • a plurality of wirings 61 a are arranged via an interlayer insulating film 62.
  • the multilayer wiring layer 61 is formed on the side opposite to the light receiving surface, and a so-called back-illuminated solid-state imaging device can be realized.
  • a support substrate 63 made of silicon, for example, is bonded to the multilayer wiring layer 61.
  • the organic photoelectric conversion unit 21 is an organic photoelectric conversion element that generates an electron / hole pair by absorbing light in a selective wavelength range (here, green light) using an organic semiconductor.
  • the organic photoelectric conversion unit 21 includes an oxygen blocking layer 41, a stabilization layer 42, an organic photoelectric conversion film 43, and a hole readout layer 44 between a pair of electrodes (lower electrode film 33 and upper electrode film 31) for extracting signal charges.
  • the organic photoelectric conversion film 32 made of is sandwiched.
  • the lower electrode film 33 and the upper electrode film 31 are electrically connected to conductive plugs 52a1 and 52b1 embedded in the semiconductor substrate 11 through a wiring layer and a contact metal layer.
  • interlayer insulating films 52A and 52B are formed on the surface S1 of the semiconductor substrate 11, and the interlayer insulating film 52A is a region facing each of the conductive plugs 52a1 and 52b1. Are provided with through holes, and conductive plugs 52a2 and 52b2 are embedded in the respective through holes. In the interlayer insulating film 52B, conductive plugs 52a3 and 52b3 are embedded in regions facing the conductive plugs 52a2 and 52b2, respectively.
  • a lower electrode film 33 is provided on the interlayer insulating film 52B, and a wiring layer 51 electrically separated by the lower electrode film 33 and the insulating film 53 is provided.
  • the organic photoelectric conversion layer 32 is formed on the lower electrode film 33, and the upper electrode film 31 and the sealing film 54 are formed so as to cover the organic photoelectric conversion layer 32.
  • a contact metal layer 55 is formed in electrical connection with the upper electrode film 31.
  • the conductive plugs 52a2 and a3 function as a connector together with the conductive plug 52a1 and form a charge (electron) transmission path from the lower electrode film 33 to the green storage layer 11G.
  • the conductive plugs 52b2 and b3 function as a connector together with the conductive plug 52b1, and together with the wiring layer 51 and the contact metal layer 55, form a discharge path for charges (electrons) from the upper electrode film 31.
  • the conductive plugs 52a2 and 52b2 are preferably composed of a laminated film of a metal material such as titanium (Ti), titanium nitride (TiN) and tungsten in order to function as a light shielding film.
  • the use of such a laminated film is desirable because contact with silicon can be ensured even when the conductive plugs 52a1 and 52b1 are formed as p-type or n-type semiconductor layers.
  • the lower electrode film 33 is provided for each pixel in a region that covers the light receiving surfaces of the inorganic photoelectric conversion units 11B and 11R formed in the semiconductor substrate 11 so as to face the light receiving surfaces.
  • the upper electrode film 31 is provided in common for each pixel.
  • a planarization film 57 is formed so as to cover the entire surface on the sealing film 54 and the contact metal layer 55.
  • an on-chip lens 58 (microlens) is provided on the planarizing film 57.
  • the on-chip lens 58 collects light incident from above on the light receiving surfaces of the organic photoelectric conversion unit 21 and the inorganic photoelectric conversion units 11B and 11R.
  • the multilayer wiring layer 61 is formed on the surface S2 side of the semiconductor substrate 11, the light receiving surfaces of the organic photoelectric conversion unit 21 and the inorganic photoelectric conversion units 11B and 11R are arranged close to each other. Thus, variations in sensitivity between colors depending on the F value of the on-chip lens 58 can be reduced.
  • a light reception signal is acquired as follows, for example.
  • the green light Lg is selectively detected (absorbed) by the organic photoelectric conversion unit 21 and subjected to photoelectric conversion.
  • holes of the generated electron / hole pairs are taken out from the lower electrode film 33 side and then accumulated in the green power storage layer 11G through the conductive plugs 52a1 to 52a3.
  • the accumulated holes are read out to the vertical signal line Lsig via a pixel transistor (not shown) during a read operation. Electrons are discharged from the upper electrode film 31 side through the contact metal layer 55, the wiring layer 51, and the conductive plugs 52b1 to 52b3.
  • blue light is absorbed and photoelectrically converted in order by the inorganic photoelectric conversion unit 11B and red light by the inorganic photoelectric conversion unit 11R.
  • the inorganic photoelectric conversion unit 11B holes corresponding to the incident blue light are accumulated in a p-type region (not shown), and the accumulated holes are read to the vertical signal line Lsig via a pixel transistor (not shown) during a read operation. It is. Electrons are accumulated in an n-type region (not shown).
  • the inorganic photoelectric conversion unit 11R holes corresponding to the incident red light are accumulated in the p-type region, and the accumulated electrons are transferred to the vertical signal line Lsig via a pixel transistor (not shown) during a read operation. Read out. Electrons are accumulated in an n-type region (not shown).
  • the organic photoelectric conversion unit 21 and the inorganic photoelectric conversion units 11B and 11R are stacking in the vertical direction, the red, green, and blue color lights are separated and detected without providing color filters. Can be obtained. Thereby, it is possible to suppress light loss (sensitivity reduction) due to color light absorption of the color filter and generation of false color associated with pixel interpolation processing.
  • an oxygen blocking layer and a stabilization layer are provided on the organic photoelectric conversion film, it is possible to select a sputtering method capable of forming a transparent electrode film having a high transmittance at a low temperature. it can.
  • the present technology may be applied to a solid-state imaging device such as a CCD (Charge Coupled Device) solid-state imaging device.
  • CCD Charge Coupled Device
  • the structure of the solid-state imaging device may be a back side illumination type or a front side illumination type.
  • the structure of the pixel in FIG. 5 is an example, and is not limited to the pixel having this structure.
  • a solid-state imaging device using an organic semiconductor device has been described so far, but other examples include an organic EL device (electroluminescence) device, an organic solar cell, and organic lighting.
  • organic EL device electroluminescence
  • organic solar cell organic solar cell
  • organic lighting In a device using an organic semiconductor film, it can be applied when a metal oxide film is formed on the organic semiconductor film.
  • FIG. 6 is a cross-sectional view illustrating an example of an organic EL unit as a semiconductor device to which the present technology is applied.
  • the organic EL unit 101 shown in FIG. 6 is used, for example, in the organic EL display of FIGS. 7 and 8 described later.
  • the organic EL unit 101 is configured to include an upper electrode film 111, an organic EL layer 112, and a lower electrode film 113.
  • the organic EL layer 112 of the present embodiment is a specific example of “semiconductor device” in the present disclosure.
  • the upper electrode film 111 and the lower electrode film 113 are basically configured in the same manner as the upper electrode film 31 and the lower electrode film 33, the description thereof will be omitted and will be omitted.
  • the organic EL layer 112 includes an oxygen blocking layer 121, a stabilization layer 122, an electron injection layer 123, an organic EL film 124, and a hole injection layer 125 in order from the top.
  • the oxygen blocking layer 121 and the stabilization layer 122 are basically configured in the same manner as the oxygen blocking layer 41 and the stabilization layer 42 in FIG. 2, description thereof is omitted because it is repeated.
  • the electron injection layer 123 injects electrons from the upper electrode film 111 into the organic EL film 124.
  • the hole injection layer 125 injects holes from the lower electrode film 113 into the organic EL film 124.
  • the organic EL film 124 is an organic film that emits light by recombination of electrons from the electron injection layer 123 and holes from the hole injection layer 125 to excite organic molecules. Although the organic EL film 124 is made of different materials, other configurations (thickness and formation method) are the same as those of the organic photoelectric conversion film 43 in FIG.
  • ⁇ Configuration example of organic EL display> 7 and 8 are cross-sectional views showing an example of the overall configuration of an organic EL display having the organic EL part of FIG.
  • FIG. 7 shows a cross-sectional example of an organic EL display 151 which is a top emission type and includes an organic EL layer 112 for each color (Red, Green, Blue).
  • the organic EL display 151 is configured by laminating a glass substrate 161, a TFT (Thin Film Transistor) 162, an organic EL unit 101 for each color, a sealing layer 163, and a sealing glass 164 in order from the bottom. .
  • TFT Thin Film Transistor
  • FIG. 8 shows a cross-sectional example of an organic EL display 201 that is a top emission type and includes the color filter 211 with the organic EL layer 112 common to each color.
  • the organic EL display 201 includes a glass substrate 161, a TFT (Thin Film Transistor) 162, an organic EL unit 101, a sealing layer 163, a color filter 211, and a sealing glass 164 in order from the bottom. Yes.
  • TFT Thin Film Transistor
  • the present technology can also be applied to an organic EL display.
  • FIG. 9 is a diagram illustrating a usage example in which the above-described solid-state imaging device is used.
  • the solid-state imaging device (image sensor) described above can be used in various cases for sensing light such as visible light, infrared light, ultraviolet light, and X-ray as follows.
  • Devices for taking images for viewing such as digital cameras and mobile devices with camera functions
  • Devices used for traffic such as in-vehicle sensors that capture the back, surroundings, and interiors of vehicles, surveillance cameras that monitor traveling vehicles and roads, and ranging sensors that measure distances between vehicles, etc.
  • Equipment used for home appliances such as TVs, refrigerators, air conditioners, etc. to take pictures and operate the equipment according to the gestures ⁇ Endoscopes, equipment that performs blood vessel photography by receiving infrared light, etc.
  • Equipment used for medical and health care ⁇ Security equipment such as security surveillance cameras and personal authentication cameras ⁇ Skin measuring instrument for photographing skin and scalp photography Such as a microscope to do beauty Equipment used for sports-Equipment used for sports such as action cameras and wearable cameras for sports applications-Used for agriculture such as cameras for monitoring the condition of fields and crops apparatus
  • the present technology is not limited to application to a solid-state imaging device, but can also be applied to an imaging device.
  • the imaging apparatus refers to a camera system such as a digital still camera or a digital video camera, or an electronic apparatus having an imaging function such as a mobile phone.
  • a module-like form mounted on an electronic device that is, a camera module is used as an imaging device.
  • the electronic apparatus 300 shown in FIG. 10 includes a solid-state imaging device (element chip) 301, an optical lens 302, a shutter device 303, a drive circuit 304, and a signal processing circuit 305.
  • a solid-state imaging device element chip
  • an optical lens 302 As the solid-state imaging device 301, the solid-state imaging device 1 according to the first embodiment of the present technology described above is provided. Thereby, the reliability of the solid-state imaging device 301 of the electronic device 300 can be improved.
  • the optical lens 302 forms image light (incident light) from the subject on the imaging surface of the solid-state imaging device 301. As a result, signal charges are accumulated in the solid-state imaging device 301 for a certain period.
  • the shutter device 303 controls the light irradiation period and the light shielding period for the solid-state imaging device 301.
  • the drive circuit 304 supplies a drive signal for controlling the signal transfer operation of the solid-state imaging device 301 and the shutter operation of the shutter device 303.
  • the solid-state imaging device 301 performs signal transfer by a drive signal (timing signal) supplied from the drive circuit 304.
  • the signal processing circuit 305 performs various signal processing on the signal output from the solid-state imaging device 301.
  • the video signal subjected to the signal processing is stored in a storage medium such as a memory or output to a monitor.
  • the configuration described as one device (or processing unit) may be divided and configured as a plurality of devices (or processing units).
  • the configurations described above as a plurality of devices (or processing units) may be combined into a single device (or processing unit).
  • a configuration other than that described above may be added to the configuration of each device (or each processing unit).
  • a part of the configuration of a certain device (or processing unit) may be included in the configuration of another device (or other processing unit). . That is, the present technology is not limited to the above-described embodiment, and various modifications can be made without departing from the gist of the present technology.
  • this technique can also take the following structures.
  • the oxygen blocking layer is made of MgF2, CaF2, BaF2, LiF, or a three-dimensional compound containing any of the MgF2, CaF2, BaF2, and LiF. (1) to (3) The semiconductor device described.
  • the semiconductor device according to any one of (1) to (9), wherein the organic film is used as an organic EL film.
  • (11) an organic film;
  • a solid-state imaging device comprising: an oxygen blocking layer that suppresses entry of oxygen into the organic film between the organic film and a metal oxide formed above the organic film.
  • (12) The solid-state imaging device according to (11), wherein the oxygen blocking layer is an inorganic fluoride having low reactivity with oxygen.
  • the oxygen blocking layer is transparent in a visible light region.
  • the oxygen blocking layer is made of MgF2, CaF2, BaF2, LiF, or a three-dimensional compound containing any of the MgF2, CaF2, BaF2, and LiF.
  • a solid-state imaging device comprising: an oxygen blocking layer that suppresses oxygen from entering the organic film, between the organic film and a metal oxide formed above the organic film; A signal processing circuit for processing an output signal output from the solid-state imaging device; And an optical system that makes incident light incident on the solid-state imaging device.
  • 1 solid-state imaging device 2 pixels, 3 pixel areas, 11 semiconductor substrate, 21 organic photoelectric conversion part, 31 upper electrode film, 32 organic photoelectric conversion layer, 33 lower electrode film, 41 oxygen blocking layer, 42 stabilization layer, 43 organic Photoelectric conversion film, 44 hole readout section, 51 wiring layer, 52A, 52B interlayer insulating film, 53 insulating film, 54 sealing film, 55 contact metal layer, 56 groove, 57 flattening film, 58 on-chip lens, 61 multilayer wiring Layer, 62 interlayer insulation film, 63 support substrate, 101 organic EL part, 111 upper electrode film, 112 organic EL layer, 113 lower electrode film, 121 oxygen blocking layer, 122 stabilization layer, 123 electron injection layer, 124 organic EL film , 125 hole injection , 151 organic EL display, 161 glass substrate, 162 TFT, 163 sealing layer, 164 sealing glass, 201 organic EL display, 211 color filter, 211 electronic device, 301 solid-state imaging device, 302 optical lens, 303 shutter device, 304 Drive

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  • Engineering & Computer Science (AREA)
  • Multimedia (AREA)
  • Signal Processing (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Solid State Image Pick-Up Elements (AREA)
  • Transforming Light Signals Into Electric Signals (AREA)
  • Light Receiving Elements (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne : un dispositif à semi-conducteurs, la fiabilité d'une couche de conversion photoélectrique organique pouvant être améliorée ; un dispositif d'imagerie à semi conducteurs ; et un dispositif électronique. Dans une partie de conversion photoélectrique organique de la présente invention, une couche de blocage de l'oxygène et une couche de stabilisation sont agencées de manière séquentielle, à partir de la partie supérieure, entre un film de conversion photoélectrique organique et un film d'électrode supérieure au-dessus du film de conversion photoélectrique organique, ledit film d'électrode supérieure étant une couche où un oxyde métallique est disposé. La couche de blocage de l'oxygène est conçue, par exemple, d'un fluorure inorganique transparent qui présente une faible réactivité à l'oxygène. La couche de blocage de l'oxygène est transparente dans la région de la lumière visible, et a une épaisseur plus épaisse que celle de la couche de stabilisation. La couche de stabilisation est conçue d'un film inorganique qui a une énergie de formation standard supérieure à celle de la couche de blocage de l'oxygène. La présente invention est applicable, par exemple, à un dispositif d'imagerie à semi-conducteurs CMOS, un film organique étant utilisé pour une partie de conversion photoélectrique.
PCT/JP2015/084739 2014-12-24 2015-12-11 Dispositif à semi-conducteurs, dispositif d'imagerie à semi-conducteurs, et dispositif électronique WO2016104173A1 (fr)

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